This invention relates to insecticidal and miticidal compositions characterized by mixing 4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-pyrrole-3-carbonitrile (hereinafter may be referred to as Compound A) and known natural pyrethroid insecticidal ingredients and/or synthetic pyrethroid insecticidal ingredients. The insecticidal and miticidal compositions of the invention can be effectively applied in the agrohorticultural field.
Compound A, which is an active ingredient of the insecticidal and miticidal composition of the invention, is an insecticidal and miticidal agent against agrohorticultural pests and is known to be effective against insects such as Hemiptera pests such as leaf-hoppers (Doltocephalidae), Lepidoptera pests such as diamond back moth (Plutella xylostella), common cutworm (Spodoptera litura) and apple leafminer (Phyllonorycter ringoniella) and Thysanoptera pests such as Thrips palmi and yellow tea thrips (Spritothrips dorsalis) and agrohorticultural pests such as mites such as two-spotted spider mite (Tetranychus urticae koch), Kanzawa spidermite (Tetranychus kanzawai kishida) and Aculops pele-kassi. 
The second active ingredient of the insecticidal and miticidal composition of the invention is a pyrethroid insecticidal ingredient, of which the following compounds are representative:
As a known natural pyrethroid insecticidal ingredient, the extracted ingredient of pyrethrum, a mixture containing (Z)-(S)-2-methyl4-oxo-3-(penta-2,4-dienyl)cyclopent-2-enyl (IR)-trans-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate (Pyrethrin I) and (Z)-(S)-2-methyl-4-oxo-3-(penta-2,4-dienyl)cyclo-pent-2-enyl (E)-(IR)-trans-3-(2-methoxycarbonylprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate (Pyrethrin II) and the like is mentioned.
As synthetic pyrethroid insecticidal ingredients,
2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether (Ethofenprox),
(RS)-xcex1-cyano-3-phenoxybenzyl (Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate (Cyhalothrin),
(RS)-xcex1-cyano4-fluoro-3-phenoxybenzyl (1RS,3RS; 1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (Cyfluthrin),
(RS)-xcex1-cyano-3-phenoxybenzyl (1RS,3RS,1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopro-panecarboxylate (Cypermethrin),
4-ethoxyphenyl[3-(4-fluoro-3-phenoxyphenyl)propyl]dimethylsilane (Silafluofen),
(S)-xcex1-cyano-3-phenoxybenzyl (1R,3S)-2,2-dimethyl-3-[(RS)1,2,2,2-tetrabromoethyl]cyclopropanecarboxylate (Tralomethrin),
2-(4-bromodifluoromethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether (Halfenprox),
2-methylbiphenyl-3-ylmethyl (Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecar-boxylate (Bifenthrin),
(RS)-xcex1-cyano-3-phenoxybenzyl 2,2,3,3-tetramethyl-cyclopropanecarboxylate (Fenpropathrin),
(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate (Fenvalerate),
(RS)-xcex1-cyano-3-phenoxybenzyl (S)-2-(4-difluoromethoxyphenyl)-3-methylbutyrate (Flucythrinate),
(RS)-xcex1-cyano-3-phenoxy-benzyl N-(2-chloro-xcex1,xcex1,xcex1,xcex1-trifluoro-p-tolyl)-D-valinate (Fluvalinate), 3-phenoxybenzyl (1RS,3RS; 1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (Permethrin) and the like are mentioned.
The above-mentioned compounds are known to be effective against agrohorticultural pests such as insects such as Hemiptera, Lepidoptera and Coleoptera insects or mites.
Hitherto, insecticidal and miticidal agents have been developed in order to control various pests such as agrohorticultural pests or hygienic pests and have been used in practice alone or in mixtures.
However, pests which have acquired resistance against various agents have been appearing as a result or the repeated use of these agents.
In particular, spider mites (Tetranychidae) have a propensity to easily develop resistance against pesticidal agents due to their ability to deposit large numbers of eggs and produce large numbers of generations which, themselves, require only a few days for development, high mutation rate and frequent inbreeding, due to minimal migration. For these reasons, two-spotted spider mite (Tetranychus urticae koch), Kanzawa spider mite (Tetranychus kanzawai kishida), Aculops pelekassi, and the like have acquired resistance, to some degree, against almost all existing pesticidal agents.
Therefore, in order to prevent and control the damage caused by spider mites, the development of a new insecticidal and miticidal agent which shows a high effect against spider mites which have acquired resistance against the conventional miticidal agents is highly desirable.
However, to invent an insecticidal and miticidal composition which shows no cross-resistance with existing insecticidal and miticidal agents, has no toxicity problems and has little negative impact on the environment, is extremely difficult. Moreover, a period of nearly ten years is required for a development of an invention.
Therefore, in order to apply an effective agent for an extended time, a rotational application of agents with different mechanisms of action has been adopted for good pest management practice. However, this approach does not necessarily give satisfactory results.
After a resistance problem has occurred, a countermeasure to resistance using a combination of insecticidal and miticidal agents has been studied. However, a high synergistic action has not always been found. On the other hand, Compound A, which is an active ingredient of the insecticidal and miticidal composition of the invention, was brought on the market quite recently and shows a high miticidal effect now even in a single use.
However, from the history of resistance problems of almost all miticidal agents in the past, it is likely that a similar problem might occur with Compound A, also.
The object of this invention is to provide a miticidal composition which demonstrates a high level of control against spider mites which have acquired resistance against Compound A
In order to provide a countermeasure to a resistance problem in spider mites against Compound A before such a problem occurs, the synergistic action with the existing insecticidal, miticidal and fungicidal agents was studied using resistant species which have been artificially established in the laboratory by selecting spider mites which have been treated with Compound A.
Thus, it has now been found that a composition which contains Compound A in combination with a pyrethroid insecticidal ingredient(s) demonstrates a joint action or synergistic effect which could not be foreseen from each individual ingredient and is very effective as an insecticidal and miticidal composition, resulting in the achievement of this invention.
Therefore, the main point of the present invention resides in insecticidal and miticidal compositions characterized by containing as active ingredients, the insecticidal and miticidal agent 4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-pyrrole-3-carbonitrile (Compound A) and a pyrethroid insecticidal ingredient(s).
Representative spider mites controlled by the present invention are: two-spotted spider mite (Tetranychus urticae koch), Tetranychus cinnabarinus (Boisduval), Kanzawa spider mite (Tetranychus Kanzawaikishida), hawthorn spider mite (Tetranychus viennensiszacher), and the like.
Advantageously, the insecticidal and miticidal composition of the invention shows not only a synergistic miticidal effect against the above-mentioned spider mites, but also demonstrates simultaneous control of troublesome pests on fruit trees, for example, citrus, apple and pear, such as leaf roller moths (Tortricidae), Carposinidae, leaf miner moths (Lyonetiidae), plant bugs (Pentatomidae), aphids (Aphididae), leafhoppers (Deltociphalidae) and thrips (Thripidae); on tea plants such as leaf roller moths, aphids and thrips; on vegetables such as diamond back moths (Plutella xylostella), Mamestra brassicae, leaf beetles (Chrysomelidae), aphids, whiteflies (Aleyrodidae), thrips and the like.
Compound A, which is an active ingredient of the insecticidal and miticidal composition of the invention, is a known compound described in Japanese Laid-open (Kokai) Patent Publication No. 104042/89 and its method of use as agrohorticultural insecticidal and miticidal agent is also shown in the Publication. It can be synthesized according to the method described therein.
On the other hand, many compounds are known as pyrethroid insecticidal ingredients, the second active ingredient of the insecticidal and miticidal composition of the invention. Their generic names and chemical names are given below. These examples, however, of not intended to limit the scope of the invention.
Generic name: Pyrethrin I
Chemical name: (Z)-(S)-2-Methyl4-oxo-3-(penta-2,4-dienyl)cyclopent-2-enyl (IR)-trans-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate
Generic name: Pyrethrin II
Chemical name: (Z)-(S)-2-Methyl4-oxo-3-(penta-2,4-dienyl)-cyclopent-2-enyl (E)-(IR)-trans-3-(2-methyloxycarbonylprop-1-enyl)-2,2-dimethylcyclopropane-carboxylate
Generic name: Ethofenprox
Chemical name: 2-(4-Ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether
Generic name: Cyhalothrin
Chemical name: (RS)-xcex1-Cyano-3-phenoxy-benzyl (Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate
Generic name: Cyfluthrin
Chemical name: (RS)-xcex1-Cyano4-fluoro-3-phenoxybenzyl (1RS,3RS; 1RS, 3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate
Generic name: Cypermethrin
Chemical name: (RS)-xcex1-Cyano-3-phenoxy-benzyl (1RS,3RS; 1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate
Generic name: Silafluofen
Chemical name: 4-Ethoxyphenyl[3-(4-fluoro-3-phenoxyphenyl)propyl]-dimethylsilane
Generic name: Tralomethrin
Chemical name: (S)-xcex1-Cyano-3-phen-oxybenzyl (1R,33S)-2,2-dimethyl-3-[(RS)1,2,2,2-tetrabromo-ethyl]cyclopropanecarboxylate
Generic name: Halfenprox
Chemical name: 2-(4-Bromodifluoro-methoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether
Generic name: Bifenthrin
Chemical name: 2-Methylbiphenyl-3-yl-methyl (Z)-(1RS,3RS)-3-(2-chloro-3,3,3-trifluoro-prop-1-enyl)-2,2-dimethyl-cyclopropanecarboxylate
Generic name: Fenpropathrin
Chemical name: (RS)-xcex1-Cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclo-propanecarboxylate
Generic name: Fenvalerate
Chemical name: (RS)-xcex1-Cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate
Generic name: Flucythrinate
Chemical name: (RS)-xcex1-Cyano-3-phenoxybenzyl (S)-2-(4-difluoromethoxy-phenyl)-3-methylbutyrate
Generic name: Fluvalinate
Chemical name: (RS)-xcex1-Cyano-3-phenoxybenzyl N-(2-chloro-xcex1,xcex1,xcex1-trifluoro-p-tolyl)-D-valinate
Generic name: Permethrin
Chemical name: 3-Phenoxybenzyl (1RS,3RS; 1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate.
The above-mentioned names of insecticidal agents are generic names described in xe2x80x9cAgrochemicals Handbook 1992 Editionxe2x80x9d (Published on Jul. 30, 1992 by Japan Plant Protection Association) and xe2x80x9cSHIBUYA INDEX-1996-(7th Edition)xe2x80x9d (Published on Apr. 1, 1996 by ZENNOH).
In this invention, among the above-mentioned, especially the extracted ingredient of pyrethrum containing Pyrethrin I and Pyrethrin II, Ethofenprox, Cyhalothrin, Cyfluthrin, Cypermethrin, Bifenthrin, Fenpropathrin, Fluvalinate, Permethrin and the like are preferable due to a high synergistic action with 4-bromo-2-(4-chloro-phenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (Compound A).
The insecticidal and miticidal composition of the invention can be formulated as a wettable powder, aqueous concentrate, emulsion, liquid concentrate, sol (flowable agent), powder, aerosol, or the like, by conventional methods such as admixing Compound A and a pyrethroid insecticidal ingredient(s) with a suitable carrier and auxiliaries, such as emulsifiers, dispersants, stabilizers, suspending agents, penetrants, and the like.
The weights (%) of the insecticidal active ingredients of the composition of the invention in the above-mentioned formulations are preferably in the range of about 1-90% for wettable powders, aqueous concentrates, emulsions, liquid concentrates and sol formulations, 0.5-10% for powder formulations, and 0.01-2% for aerosol formulations.
Carriers suitable for use in the invention may be any solid or liquid carrier which is commonly used for an agrohorticultural composition and are not limited to specific substances. Various surfactants, stabilizers and other auxiliary ingredients may be used in the formulations, as necessary.
The insecticidal and miticidal composition of the invention may also be present in commercially useful formulations or application forms prepared from these formulations as a mixture with other active compounds, for example various insecticidal, miticidal, fungicidal and herbicidal agents, plant growth regulators, repellents, attractants, synergists and fertilizers and fragrances, in order to expand the applicability of the insecticidal and miticidal composition of the invention.
The mixing ratio of Compound A and the active ingredient of known pyrethroid insecticidal agent(s) are generally as follows. The ratio of the latter to 1 weight part of the former is generally 0.01-100 weight parts, and preferably is 0.5-20 weight parts.
The application method of the insecticidal and miticidal composition of the invention is as follows. Although the application amount may differ according to the numbers of pests or mites and the kinds and cultivation form of the target crop, the amount of active ingredients (total amount of Compound A and the active ingredient of known pyrethroid insecticidal agent(s)) is generally 0.1-1,000 g and preferably, 40-500 g, per 10 acres. In the case of wettable powders, aqueous concentrates, emulsions, liquid concentrates and sols, they may be diluted with water and applied to the crop at an application rate of 100-700 liters per 10 acres. In the case of powders or aerosols, the crop may be treated with the undiluted formulation.